Ru/MgO catalyst with dual Ru structure sites for efficient CO production from CO2 hydrogenation

Xie, Shaohua; Ye, Kailong; Du, Jingshan S.; Zhang, Xing; Kim, Daekun; Loukusa, Jeremia; Ma, Lu; Ehrlich, Steven N.; Marinkovic, Nebojsa S.; De Yoreo, James J.; Liu, Fudong

doi:10.1016/j.cej.2024.150486

Ru/MgO catalyst with dual Ru structure sites for efficient CO production from CO₂ hydrogenation

Journal Article · Sat Mar 16 00:00:00 EDT 2024 · Chemical Engineering Journal

DOI:https://doi.org/10.1016/j.cej.2024.150486· OSTI ID:2336718

Xie, Shaohua ^[1]; Ye, Kailong ^[1]; Du, Jingshan S. ^[2]; Zhang, Xing ^[1]; Kim, Daekun ^[1]; Loukusa, Jeremia ^[1]; Ma, Lu ^[3]; Ehrlich, Steven N. ^[3]; Marinkovic, Nebojsa S. ^[4]; De Yoreo, James J. ^[5]; ^[6]

Univ. of Central Florida, Orlando, FL (United States)
Pacific Northwest National Laboratory (PNNL), Richland, WA (United States)
Brookhaven National Laboratory (BNL), Upton, NY (United States)
Columbia Univ., New York, NY (United States)
Pacific Northwest National Laboratory (PNNL), Richland, WA (United States); Univ. of Washington, Seattle, WA (United States)
Univ. of California, Riverside, CA (United States); Univ. of Central Florida, Orlando, FL (United States)

The development and comprehension of supported metal catalysts for CO₂ hydrogenation is of paramount importance in mitigating the net CO₂ emissions. Supported Ru catalysts have been widely recognized in facilitating CO₂ methanation, on which recent findings suggest that the CO₂ hydrogenation process can be manipulated to favor the reverse water–gas shift (RWGS) pathway by precisely adjusting the size of Ru particles. However, the size-dependent impact of Ru remains a topic of lively debate. In this work, Ru/MgO catalysts with Ru in the form of single atoms (Ru₁) and few-atom cluster (Ru_FAC) structures were prepared for CO₂ hydrogenation. The 1.0Ru/MgO catalyst (with 1 wt.% of Ru), featuring a mixture of Ru₁ and Ru_FAC with a size of 0.6–1.0 nm, showed the highest CO yield (38% at 500 °C) with balanced CO₂ conversion and CO selectivity. Transient CO₂ hydrogenation and temperature-programmed surface reaction (TPSR) studies suggested that the adsorbed CO₂ species participated in CO₂ hydrogenation. On Ru₁ sites, CO₂ hydrogenation followed the RWGS pathway, resulting in the production of CO. In contrast, on Ru_FAC sites, the enhanced H₂ dissociation ability, along with the presence of adsorbed bidentate and monodentate carbonate species at the Ru-MgO interfaces, facilitated the formation of CH₄ through the CO₂ methanation pathway. In conclusion, this study highlights the critical roles of Ru structure and local environment in defining the CO₂ hydrogenation pathways and provides new design principles for highly active Ru-based catalysts.

View Accepted Manuscript (DOE)

Research Organization:: Pacific Northwest National Laboratory (PNNL), Richland, WA (United States)

Sponsoring Organization:: National Science Foundation (NSF); USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities (SUF); USDOE Office of Science (SC), Biological and Environmental Research (BER)

Grant/Contract Number:: AC05-76RL01830; SC0012704

OSTI ID:: 2336718

Report Number(s):: PNNL-SA--192165

Journal Information:: Chemical Engineering Journal, Journal Name: Chemical Engineering Journal Vol. 487; ISSN 1385-8947

Publisher:: ElsevierCopyright Statement

Country of Publication:: United States

Language:: English

References (46)

Ru-based catalysts for efficient CO2 methanation: Synergistic catalysis between oxygen vacancies and basic sites Wang, Chunfen; Lu, Yonglian; Zhang, Yu Nano Research, Vol. 16, Issue 10 https://doi.org/10.1007/s12274-023-5592-3	journal	March 2023
Methanation of CO, CO2 and selective methanation of CO, in mixtures of CO and CO2, over ruthenium carbon nanofibers catalysts Jiménez, Vicente; Sánchez, Paula; Panagiotopoulou, Paraskevi Applied Catalysis A: General, Vol. 390, Issue 1-2 https://doi.org/10.1016/j.apcata.2010.09.026	journal	December 2010
Highly-selective CO2 conversion via reverse water gas shift reaction over the 0.5wt% Ru-promoted Cu/ZnO/Al2O3 catalyst Zhuang, Yichen; Currie, Robert; McAuley, Kimberley B. Applied Catalysis A: General, Vol. 575 https://doi.org/10.1016/j.apcata.2019.02.016	journal	April 2019
Decoupling the effect of Ni particle size and surface oxygen deficiencies in CO2 methanation over ceria supported Ni Hao, Ziwen; Shen, Jindong; Lin, Shuangxi Applied Catalysis B: Environmental, Vol. 286 https://doi.org/10.1016/j.apcatb.2021.119922	journal	June 2021
Atomically dispersed Pt/CeO2 catalyst with superior CO selectivity in reverse water gas shift reaction Zhao, Zhiying; Wang, Mingzhi; Ma, Peijie Applied Catalysis B: Environmental, Vol. 291 https://doi.org/10.1016/j.apcatb.2021.120101	journal	August 2021
Recent progress in syngas production via catalytic CO2 hydrogenation reaction Bahmanpour, Ali M.; Signorile, Matteo; Kröcher, Oliver Applied Catalysis B: Environmental, Vol. 295 https://doi.org/10.1016/j.apcatb.2021.120319	journal	October 2021
Role of interfacial oxygen vacancies in low-loaded Au-based catalysts for the low-temperature reverse water gas shift reaction Rabee, Abdallah. I. M.; Zhao, Dan; Cisneros, Sebastian Applied Catalysis B: Environmental, Vol. 321 https://doi.org/10.1016/j.apcatb.2022.122083	journal	February 2023
Mechanistic insights into chemical reduction of CO2 by reverse water-gas shift reaction on Ru(0001) surface: The water promotion effect Sathishkumar, Nadaraj; Wu, Shiuan-Yau; Chen, Hsin-Tsung Applied Surface Science, Vol. 581 https://doi.org/10.1016/j.apsusc.2021.152354	journal	April 2022
Nano-faceted stabilization of polar-oxide thin films: The case of MgO(111) and NiO(111) surfaces Kerrigan, A.; Pande, K.; Pingstone, D. Applied Surface Science, Vol. 596 https://doi.org/10.1016/j.apsusc.2022.153490	journal	September 2022
Methanation of carbon dioxide on Ru/Al2O3: Catalytic activity and infrared study Garbarino, Gabriella; Bellotti, Daria; Finocchio, Elisabetta Catalysis Today, Vol. 277 https://doi.org/10.1016/j.cattod.2015.12.010	journal	November 2016
Effect of metal loading on the CO2 methanation: A comparison between alumina supported Ni and Ru catalysts Quindimil, Adrián; De-La-Torre, Unai; Pereda-Ayo, Beñat Catalysis Today, Vol. 356 https://doi.org/10.1016/j.cattod.2019.06.027	journal	October 2020
CO2 hydrogenation over Ru hydrotalcite-derived catalysts Misol, Alexander; Giarnieri, Ilenia; Ospitali, Francesca Catalysis Today, Vol. 425 https://doi.org/10.1016/j.cattod.2023.114362	journal	January 2024
Carbon dioxide adsorption on oxide nanoparticle surfaces Baltrusaitis, Jonas; Schuttlefield, Jennifer; Zeitler, Elizabeth Chemical Engineering Journal, Vol. 170, Issue 2-3 https://doi.org/10.1016/j.cej.2010.12.041	journal	June 2011
Elevated temperature CO2 capture on nano-structured MgO–Al2O3 aerogel: Effect of Mg/Al molar ratio Han, Seung Ju; Bang, Yongju; Kwon, Hyuk Jae Chemical Engineering Journal, Vol. 242 https://doi.org/10.1016/j.cej.2013.12.092	journal	April 2014
Controlled synthesis of MgO with diverse basic sites and its CO2 capture mechanism under different adsorption conditions Gao, Wanlin; Zhou, Tuantuan; Wang, Qiang Chemical Engineering Journal, Vol. 336 https://doi.org/10.1016/j.cej.2017.12.025	journal	March 2018
Ru/K2CO3–MgO catalytic sorbent for integrated CO2 capture and methanation at low temperatures Jo, Seongbin; Son, Han Dong; Kim, Tae-Young Chemical Engineering Journal, Vol. 469 https://doi.org/10.1016/j.cej.2023.143772	journal	August 2023
CO2 methanation on Ru-doped ceria Sharma, Sudhanshu; Hu, Zhenpeng; Zhang, Peng Journal of Catalysis, Vol. 278, Issue 2 https://doi.org/10.1016/j.jcat.2010.12.015	journal	March 2011
Catalytic behavior of supported Ru nanoparticles on the {1 0 0}, {1 1 0}, and {1 1 1} facet of CeO2 Wang, Fei; Li, Changming; Zhang, Xiaoyu Journal of Catalysis, Vol. 329 https://doi.org/10.1016/j.jcat.2015.05.014	journal	September 2015
Influence of pretreatment temperature on catalytic performance of rutile TiO2-supported ruthenium catalyst in CO2 methanation Xu, Jinghua; Su, Xiong; Duan, Hongmin Journal of Catalysis, Vol. 333 https://doi.org/10.1016/j.jcat.2015.10.025	journal	January 2016
Mechanism of CO2 reduction by H2 on Ru(0 0 0 1) and general selectivity descriptors for late-transition metal catalysts Avanesian, Talin; Gusmão, Gabriel S.; Christopher, Phillip Journal of Catalysis, Vol. 343 https://doi.org/10.1016/j.jcat.2016.03.016	journal	November 2016
CO2 methanation using metals nanoparticles supported on high surface area MgO Goodarzi, Farnoosh; Kock, Mikkel; Mielby, Jerrik Journal of CO2 Utilization, Vol. 69 https://doi.org/10.1016/j.jcou.2023.102396	journal	March 2023
Recent trends in developments of active metals and heterogenous materials for catalytic CO2 hydrogenation to renewable methane: A review Fan, Wei Keen; Tahir, Muhammad Journal of Environmental Chemical Engineering, Vol. 9, Issue 4 https://doi.org/10.1016/j.jece.2021.105460	journal	August 2021
A nonlinear filtering algorithm for denoising HR(S)TEM micrographs Du, Hongchu Ultramicroscopy, Vol. 151 https://doi.org/10.1016/j.ultramic.2014.11.012	journal	April 2015
Adsorption and Dissociation of CO₂ on Ru(0001) Pachecka, M.; Sturm, J. M.; Lee, C. J. The Journal of Physical Chemistry C, Vol. 121, Issue 12 https://doi.org/10.1021/acs.jpcc.7b00021	journal	March 2017
Experimental and Computational Synergistic Design of Cu and Fe Catalysts for the Reverse Water–Gas Shift: A Review Pahija, Ergys; Panaritis, Christopher; Gusarov, Sergey ACS Catalysis, Vol. 12, Issue 12 https://doi.org/10.1021/acscatal.2c01099	journal	May 2022
Low-Temperature CO ₂ Methanation over CeO ₂ -Supported Ru Single Atoms, Nanoclusters, and Nanoparticles Competitively Tuned by Strong Metal–Support Interactions and H-Spillover Effect Guo, Yu; Mei, Sheng; Yuan, Kun ACS Catalysis, Vol. 8, Issue 7 https://doi.org/10.1021/acscatal.7b04469	journal	May 2018
Ru-Catalyzed Reverse Water Gas Shift Reaction with Near-Unity Selectivity and Superior Stability Tang, Rui; Zhu, Zhijie; Li, Chaoran ACS Materials Letters, Vol. 3, Issue 12 https://doi.org/10.1021/acsmaterialslett.1c00523	journal	October 2021
In Situ FTIR Spectroscopic Analysis of Carbonate Transformations during Adsorption and Desorption of CO ₂ in K-Promoted HTlc Du, Hai; Williams, Christopher T.; Ebner, Armin D. Chemistry of Materials, Vol. 22, Issue 11 https://doi.org/10.1021/cm100703e	journal	June 2010
CO ₂ Reduction on Supported Ru/Al ₂ O ₃ Catalysts: Cluster Size Dependence of Product Selectivity Kwak, Ja Hun; Kovarik, Libor; Szanyi, János ACS Catalysis, Vol. 3, Issue 11 https://doi.org/10.1021/cs400381f	journal	October 2013
MgO/Al₂O₃ Sorbent for CO₂ Capture Li, Lei; Wen, Xia; Fu, Xin Energy & Fuels, Vol. 24, Issue 10 https://doi.org/10.1021/ef100817f	journal	September 2010
Overturning CO₂ Hydrogenation Selectivity with High Activity via Reaction-Induced Strong Metal–Support Interactions Xin, Hui; Lin, Le; Li, Rongtan Journal of the American Chemical Society, Vol. 144, Issue 11 https://doi.org/10.1021/jacs.1c12603	journal	March 2022
Active Site Dependent Reaction Mechanism over Ru/CeO ₂ Catalyst toward CO ₂ Methanation Wang, Fei; He, Shan; Chen, Hao Journal of the American Chemical Society, Vol. 138, Issue 19 https://doi.org/10.1021/jacs.6b02762	journal	May 2016
Tuning Selectivity of CO ₂ Hydrogenation Reactions at the Metal/Oxide Interface Kattel, Shyam; Liu, Ping; Chen, Jingguang G. Journal of the American Chemical Society, Vol. 139, Issue 29 https://doi.org/10.1021/jacs.7b05362	journal	July 2017
Low-Temperature Restructuring of CeO ₂ -Supported Ru Nanoparticles Determines Selectivity in CO ₂ Catalytic Reduction Aitbekova, Aisulu; Wu, Liheng; Wrasman, Cody J. Journal of the American Chemical Society, Vol. 140, Issue 42 https://doi.org/10.1021/jacs.8b07615	journal	September 2018
Adsorption and Reaction of CO ₂ on the RuO ₂ (110) Surface Wang, Y.; Lafosse, A.; Jacobi, K. The Journal of Physical Chemistry B, Vol. 106, Issue 21 https://doi.org/10.1021/jp025619x	journal	May 2002
Lewis Acido-Basic Interactions between CO ₂ and MgO Surface: DFT and DRIFT Approaches Cornu, Damien; Guesmi, Hazar; Krafft, Jean-Marc The Journal of Physical Chemistry C, Vol. 116, Issue 11 https://doi.org/10.1021/jp211171t	journal	March 2012
Interfacial compatibility critically controls Ru/TiO2 metal-support interaction modes in CO2 hydrogenation Zhou, Jun; Gao, Zhe; Xiang, Guolei Nature Communications, Vol. 13, Issue 1 https://doi.org/10.1038/s41467-021-27910-4	journal	January 2022
CO ₂ methanation by Ru-doped ceria: the role of the oxidation state of the surface Upham, D. Chester; Derk, Alan R.; Sharma, Sudanshu Catalysis Science & Technology, Vol. 5, Issue 3 https://doi.org/10.1039/C4CY01106F	journal	January 2015
Methanation of CO ₂ and reverse water gas shift reactions on Ni/SiO ₂ catalysts: the influence of particle size on selectivity and reaction pathway Wu, H. C.; Chang, Y. C.; Wu, J. H. Catalysis Science & Technology, Vol. 5, Issue 8 https://doi.org/10.1039/C5CY00667H	journal	January 2015
Catalytic reduction of CO ₂ by H ₂ for synthesis of CO, methanol and hydrocarbons: challenges and opportunities Porosoff, Marc D.; Yan, Binhang; Chen, Jingguang G. Energy & Environmental Science, Vol. 9, Issue 1 https://doi.org/10.1039/C5EE02657A	journal	January 2016
Selective CO ₂ methanation on Ru/TiO ₂ catalysts: unravelling the decisive role of the TiO ₂ support crystal structure Kim, A.; Sanchez, C.; Patriarche, G. Catalysis Science & Technology, Vol. 6, Issue 22 https://doi.org/10.1039/C6CY01677D	journal	January 2016
Mesoporous CoO-supported palladium nanocatalysts with high performance for o-xylene combustion Xie, Shaohua; Liu, Yuxi; Deng, Jiguang Catalysis Science & Technology, Vol. 8, Issue 3 https://doi.org/10.1039/C7CY02007D	journal	January 2018
CO2 methanation property of Ru nanoparticle-loaded TiO2 prepared by a polygonal barrel-sputtering method Abe, Takayuki; Tanizawa, Masaaki; Watanabe, Kuniaki Energy & Environmental Science, Vol. 2, Issue 3 https://doi.org/10.1039/b817740f	journal	January 2009
Recent advances in catalytic hydrogenation of carbon dioxide Wang, Wei; Wang, Shengping; Ma, Xinbin Chemical Society Reviews, Vol. 40, Issue 7 https://doi.org/10.1039/c1cs15008a	journal	January 2011
Structure of the hydrogen-stabilized MgO ( 111 ) − ( 1 × 1 ) polar surface: Integrated experimental and theoretical studies Lazarov, V. K.; Plass, R.; Poon, H-C. Physical Review B, Vol. 71, Issue 11 https://doi.org/10.1103/PhysRevB.71.115434	journal	March 2005
Highly active copper-ceria and copper-ceria-titania catalysts for methanol synthesis from CO2 Graciani, J.; Mudiyanselage, K.; Xu, F. Science, Vol. 345, Issue 6196 https://doi.org/10.1126/science.1253057	journal	July 2014

Similar Records

CO₂ methanation reaction pathways over unpromoted and NaNO₃-promoted Ru/Al₂O₃ catalysts

Journal Article · Wed Jun 08 20:00:00 EDT 2022 · Catalysis Science and Technology · OSTI ID:1885245

FTIR spectroscopic study of the interaction of CO[sub 2] and CO[sub 2] + H[sub 2] over partially oxidized Ru/TiO[sub 2] catalyst

Journal Article · Mon Feb 28 23:00:00 EST 1994 · Journal of Catalysis; (United States) · OSTI ID:7034802

Low-Temperature Restructuring of CeO₂-Supported Ru Nanoparticles Determines Selectivity in CO₂ Catalytic Reduction

Journal Article · Mon Sep 24 20:00:00 EDT 2018 · Journal of the American Chemical Society · OSTI ID:1484844

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
CO2 hydrogenation
Few-atom cluster structure
Reaction mechanism
Ru/MgO
Single-atom catalyst

Ru/MgO catalyst with dual Ru structure sites for efficient CO production from CO2 hydrogenation

Citation Formats

References (46)

Similar Records

Related Subjects

Ru/MgO catalyst with dual Ru structure sites for efficient CO production from CO₂ hydrogenation